Bisazomethine metal complexes

ABSTRACT

Disclosed are pigment dyes containing the basic structure of formula I, ##SPC1## 
     in which R 1  is alkyl, 
     R 2  is alkylcarbonyl, alkoxycarbonyl or -CONR 6  R 7 , 
     R.sub. 3 is hydrogen or alkyl 
     R 4  is an aromatic carbo- or heterocyclic bivalent radical bound through ortho or peri-positions 
     R 5 , together with &gt;C=C&lt; group, signifies an aromatic carbo- or heterocyclic ring, 
     R 6  is hydrogen or alkyl, 
     R 7  is hydrogen, alkyl or a mono- or bi-nuclear aromatic carbo- or heterocyclic ring, and 
     Me is a bivalent transition metal atom or zinc, 
     Their production and use in pigmenting, for example, plastics, synthetic resins, paints, varnishes, paper, viscose and cellulose acetate.

The invention relates to bisazomethine metal complexes.

Thus, the invention provides pigment dyes containing the basic structureof formula I, ##SPC2##

in which R₁ is alkyl,

R₂ is alkylcarbonyl, alkoxycarbonyl or -CONR₆ R₇,

R₃ is hydrogen or alkyl

R₄ is an aromatic carbo- or heterocyclic bivalent radical bound throughortho or peri-positions

R₅, together with the >C=C< group, signifies an aromatic carbo- orheterocyclic ring,

R₆ is hydrogen or alkyl,

R₇ is hydrogen, alkyl or a mono- or bi-nuclear aromatic carbo- orheterocyclic ring, and

Me is a bivalent transition metal atom or zinc.

The basic structure of formula I may be substituted in any of thearomatic nuclei, and such nuclei may have further nuclei fused thereto,any substituent, however, being chosen so as not deleteriously to affectthe pigment properties of the compounds, suitable examples beinghereinafter given. The compounds may also bear a carboxy group as one ofsaid substituents. Any alkyl radical or moiety in the basic structure offormula I is preferably of 1 to 4 carbon atoms.

Representative of the compounds provided by the invention are thecompounds of formula Ia, ##SPC3##

Where

R₉ is hydrogen or methyl,

R₁₀ is C₁₋₂ alkyl, C₁₋₂ alkoxy or --NHR₁₃,

r₁₁ is 1,2-phenylene, unsubstituted or substituted as hereinafter setforth, 1,2-, 2,3- or 1,8-naphthylene, 9,10-phenanthrylene,5,6-acenaphthenylene or a radical of formula (a), (b), (c), (d) or (e),##SPC4##

R₁₂ signifies a radical of formula (f), (g), (h), (i) or (j), ##EQU1##WHEREIN THE ASTERISKED ATOM IS BOUND TO THE CARBON ADJACENT THE OXYGENIN FORMULA Ia, radicals (f) and (g) being unsubstituted or substitutedas hereinafter set forth,

R₁₃ signifies hydrogen, C₁₋₄ alkyl, naphthyl, benzimidazolonyl-5 orphenyl, or phenyl substituted by up to three substituents selected frommethyl (up to 3 thereof), chlorine, bromine, nitro and C₁₋₂ alkoxy (upto 2 thereof), C₁₋₂ alkylcarbonylamino, phenylcarbonylamino andphenylaminocarbonyl (up to 1 thereof), which latter two radicals areunsubstituted or substituted as hereinafter set forth,

R₁₄ is methyl or phenyl,

R₁₅ is hydrogen, methyl or phenyl, and

Me₁ is nickel, copper, zinc or cobalt,

any substituted phenylene as R₁₁, any phenylcarbonylamino orphenylaminocarbonyl in R₁₃ and any substituted radical (f) or (g) as R₁₂being substituted by up to two substituents selected from chlorine,bromine, methyl and C₁₋₂ alkoxy (up to two thereof), cyano, hydroxy,nitro, C₁₋₂ alkoxycarbonyl, aminocarbonyl, C₁₋₂ alkylaminocarbonyl,di-C₁₋₂ alkylaminocarbonyl, carboxyl, phenyl and phenoxy (up to 1thereof).

In the compounds of formula Ia, R₉ is preferably hydrogen. Any C₁₋₂alkyl as R₁₀ is preferably methyl. R₁₃ is preferably hydrogen, C₁₋₂alkyl, benzimidazolonyl-5 or optionally substituted phenyl, any phenylas R₁₃ preferably being unsubstituted or substituted by up to 3substituents selected from methyl (up to 3), chlorine, bromine, nitroand C₁₋₂ alkoxy (up to 2 from this group) and C₁₋₂ alkylcarbonylamino,phenylcarbonylamino and phenylaminocarbonyl (up to one from this group),any phenyl group in said latter two radicals being unsubstituted orsubstituted by up to two substituents selected from chlorine, bromineand C₁₋₂ alkoxy. Preferably R₁₀ is unsubstitutedbenzimidazolonyl-5-amino or phenylamino in which the phenyl isunsubstituted or substituted as indicated above to be preferred. Morepreferably R₁₀ is unsubstituted phenylamino or phenylamino substitutedby one or two methoxy groups and/or by a methyl or chlorine. R₁₁ ispreferably a 1,2-phenylene radical, unsubstituted or substituted by upto two substituents as defined above, a radical of formula (a), above,or a radical of formula (c), above, any 1,2-phenylene preferably beingunsubstituted or mono-substituted by chlorine, bromine, methyl, methoxy,or nitro, more preferably being unsubstituted or mono substituted bychlorine, methyl or methoxy.

Where R₁₂ signifies an optionally substituted radical of formula (f),such is preferably unsubstituted or substituted by one or twosubstituents selected from chlorine, bromine and methoxy (up to twothereof) or nitro (up to one thereof). More preferably it isunsubstituted.

Where R₁₂ signifies an optionally substituted radical of formula (g),such is preferably of formula (g'), ##SPC5##

where R₂₀ is hydrogen or carboxy and R₂₁ is hydrogen, chlorine, bromineor nitro, preferably hydrogen.

Where R₁₂ signifies a radical of formula (h), R₁₄, therein, ispreferably methyl.

Where R₁₂ signifies a radical of formula (j), R₁₄, therein, ispreferably methyl and R₁₅, therein, is preferably phenyl.

Of the radicals (f) to (j) as R₁₂, the radicals (f), (g), (h) and (i)are more preferred, particularly the radicals (g), (h) and (i).

In the compounds of formula Ia, Me, preferably signifies nickel orcopper, most preferably nickel.

As a preferred class of compounds of formula Ia may be given thecompounds of formula Ib, ##SPC6##

in which

A is methyl, C₁₋₂ alkoxy, --NH₂, C₁₋₂ alkylamino,benzimidazolonyl-5-amino or phenylamino, said phenylamino beingunsubstituted or substituted by up to three substituents selected frommethyl (up to 3 thereof), chlorine, bromine, nitro and C₁₋₂ alkoxy (upto 2 thereof), C₁₋₂ alkylcarbonylamino, phenylcarbonylamino andphenylaminocarbonyl (up to 1 thereof), the phenyls in saidphenylcarbonylamino and phenylaminocarbonyl groups being unsubstitutedor substituted by up to two substituents selected from chlorine, bromineand C₁₋₂ alkoxy,

B signifies unsubstituted 2,3-dihydroxyquinoxalinylene-6,7,benzidimazolonylene-5,6 or 1,2-phenylene, or 1,2-phenylene substitutedby up to two substituents selected from chlorine, bromine, methyl andC₁₋₂ alkoxy (up to 2 thereof), cyano, hydroxy, nitro, C₁,2-alkoxycarbonyl, aminocarbonyl and carboxy (up to 1 thereof),

D signifies a radical (f) above, unsubstituted or substituted by up totwo substituents selected from chlorine, bromine and methoxy (up to 2thereof), and nitro (up to 1 thereof); a radical of formula (i), above,a radical of formula (g'), above, a radical of formula (h), in which R₁₄is methyl, or a radical of formula (j), in which R₁₄ is methyl and R₁₅is phenyl,

and Me₂ is nickel or copper.

As a further preferred class of compounds may be given the compounds offormula Ic, ##SPC7##

where

A₁ is unsubstituted benzimidazolonyl-5-amino, unsubstituted phenylaminoor phenylamino substituted by up to three substituents selected frommethyl (up to 3 thereof), chlorine, bromine, nitro, C₁₋₂ alkoxy (up to 2thereof), C₁₋₂ alkylcarbonylamino, phenylcarbonylamino andphenylaminocarbonyl (up to 1 thereof), any phenyl moiety in said lattertwo radicals being unsubstituted or substituted by up to twosubstituents selected from chlorine, bromine and C₁₋₂ alkoxy,

B₁ signifies unsubstituted benzimidazolonylene-5,6, or 1,2-phenylene,unsubstituted or mono-substituted by chlorine, bromine, methyl, methoxyor nitro,

D₁ signifies an unsubstituted radical (f), above, a radical (g'), above,where R₂₁ is hydrogen, a radical (h), above, where R₁₄ is methyl, or aradical (i), above,

and Me₂ is as defined above.

As a still further preferred class of compounds may be given in thecompounds of formula Id, ##SPC8##

where

A₂ is phenylamino, unsubstituted or substituted by one or two methoxygroups and/or by a chlorine or methyl,

B₂ is unsubstituted benzimidazolonylene-5,6,or 1,2-phenylene,unsubstituted or mono-substituted by chlorine, methyl or methoxy,

D₂ is a radical (g'), above, in which R₂₁ is hydrogen, a radical (h),above, where R₁₄ is methyl, or a radical (i), above, and

Me₃ is nickel.

Where, in formula Id, A₂ is phenylamino substituted by two methoxygroups, such are preferably in positions 2 and 5 of the phenyl ring. Anysingle methoxy substituent is preferably in position 2 of said ring.

The invention also provides a process for the production of pigment dyescontaining the basic structure of formula I, above, which processcomprises a) metallizing a compound having the basic structure offormula II, ##SPC9##

in which R₁ to R₅ are as defined above,

by reaction with a salt of a bivalent transition metal or of zinc, or b)condensing a diamine of formula III,

    h.sub.2 n--r.sub.4 --nh.sub.2

where R₄ is as defined above,

with an ortho-hydroxyaldehyde of formula IV, ##EQU2## in which R₅ is asdefined above, and with a compound of formula V ##EQU3## in which R₁ toR₃ are as defined above, and

R₈ is alkyl (preferably of 1 to 4 carbon atoms) or hydrogen,

in the presence of a salt of a bivalent transition metal or of zinc, orc) condensing an ortho-hydroxyaldehyde of formula IV, with a compound offormula VI, ##EQU4## in which R₁ to R₄ are as defined above, in thepresence of a salt of a bivalent transition metal or of zinc.

The preferred transition metal and zinc salts employed in the aboveprocesses (a), (b) and (c) are the hydrosoluble salts, e.g. thechlorides, sulphates, nitrates, formates and acetates, the latter beingespecially preferred.

The metallisation reaction in process (a) may be carried out inconventional manner, e.g. with the compound of formula II dissolved in asolvent, e.g. in N,N-dimethyl formamide, or in suspension form. Thecompounds of formula II have low solubility in water, alcohols, ketonesand hydrocarbons.

The condensation reaction in processes (b) and (c) is convenientlycarried out in conventional manner. Suitably, condensation is carriedout in an inert solvent, e.g. in water, an alcohol, glycol or glycolether containing up to 4 carbon atoms, or in dimethylformamide. Asuitable temperature is from 20° to 150°C, preferably from 40° to 100°C.

The resulting products may be isolated and purified in conventionalmanner, isolation conveniently being effected by precipitation fromreaction media in which the products are insoluble. Wheredimethylformamide is employed as reaction medium, precipitation isconveniently effected by adding water to the hot medium until a turbidsolution forms, followed by cooling and filtration.

The compounds of formula II are new and form a further aspect of thepresent invention. They may be obtained employing process (b) or (c),above, in the absence of the transition metal or zinc salt.

The compounds of formula VI are also new and form a further aspect ofthe invention. They may be produced by condensing a compound of formulaIII, above, with a compound of formula VII, ##EQU5## in which R₁ to R₃and R₈ are as defined above.

The above processes for producing compounds II and VI are convenientlycarried out under the same conditions as processes (b) and (c).

The pigments of formula I are suitable for pigmenting plastics orsynthetic resins in the mass, (e.g. polyethylene, polystyrene, p.v.c.and synthetic leathers), either free from or containing solvents. Theymay also be employed as pigments in paints, of an oil or water base, invarnishes, for spin dyeing viscose or cellulose acetate, and forpigmenting rubber. They may also be used in printing in the graphicaltrade, for mass dyeing of paper, for coating textiles, and for pigmentprinting.

The dyeings obtained have notable fastness to heat, light, weathering,migration and solvents, and have a good depth of colour. The compoundshave good application properties, e.g. resistance to flocculation andcrystallisation and good dispersibility and covering capacity.

The pigment properties may be further improved by treatment of the crudepigments in organic solvents at elevated temperatures, e.g. 110° to200°C. The organic solvents (in which the pigments themselves are notdissolved) may be, for example, chlorobenzenes (mixtures), nitrobenzene,dimethylformamide, glacial acetic acid, ethylene glycol or quinoline.

In the following Examples, the parts and percentages are by weight andthe temperatures in degrees centigrade.

EXAMPLE 1

24.6 Parts of 5,6-diaminobenzimidazolone are suspended in 190 parts ofboiling methanol. To this mixture 35 parts ofα-ethoxymethylene-acetoacetanilide, dissolved in 240 parts of warmmethanol, are added slowly and with stirring. The suspension is boiledat reflux for 6 hours, cooled, and the residue filtered off and washedwith ethanol. After drying in a vacuum at 70°, the yellow product offormula ##SPC10##

is obtained in good yields.

17.6 Parts of the above product are dissolved in 140 parts ofN,N-dimethyl formamide at 90°. A solution of 8.6 parts of2-hydroxy-1-naphthaldehyde in 50 parts of N,N-dimethyl formamide areslowly added, the mixture is heated to 130° over the course of 3 hourswith stirring, cooled to 5° and the obtained precipitate is filteredoff, washed with N,N-dimethyl formamide and ethanol and dried at 70° ina vacuum. The yellow product of formula ##SPC11##

has a M.P. of 297°-298° with decomposition.

7.6 Parts of this product are heated to 130° in 75 parts of N,N-dimethylformamide. 4 Parts of nickel acetate tetrahydrate in 85 parts ofN,N-dimethyl formamide are added dropwise with stirring, heated to 130°and the suspension is stirred at 130°-140° over the course of 4 hours.After cooling the mixture is filtered off and washed with N,N-dimethylformamide and subsequently with ethanol until the ethanol filtrate iscolourless. After drying in a vacuum at 70°, a red pigment of forumla##SPC12##

is obtained which in varnishes and PVC gives red dyeings with goodfastness properties.

EXAMPLE 2

Following Example 1 but using 3.2 parts of copper acetate-monohydrate inplace of nickel acetate tetrahydrate, the brown copper complex ofanalogous structure is obtained.

EXAMPLE 3

Replacing in Example 1 the 2-hydroxy-1-naphthaldehyde by an equimolaramount of 3-cyano-2,6-dihydroxy-5-formyl-4-methyl-pyridine, a product offormula ##SPC13##

is obtained in similar manner. In varnishes and PVC it shows fastreddish brown dyeings.

EXAMPLE 4

Replacing, in Example 1, the 5,6-diaminobenzimidazolone by 16.2 parts ofo-phenylene diamine, a product of formula ##SPC14##

is obtained in analogous manner as intermediate product.

8.9 Parts of this product are dissolved with heating in 640 parts ofethanol. A suspension of 5.3 parts of3-cyano-2,6-dihydroxy-5-formyl-4-methyl-pyridine in 200 parts of ethanolare slowly added and the mixture is heated to the boil. After stirringfor 30 minutes at reflux, 7.5 parts of nickel acetate tetrahydrate in280 parts of ethanol are slowly added. The reaction mixture is stirredat reflux for 6 further hours, cooled, filtered off by suction andwashed with ethanol. After drying at 70° in a vacuum, an orange-yellowpigment of formula ##SPC15##

is obtained which has good fastness properties in varnishes and PVC.

EXAMPLE 5

Replacing, in Example 4, the α-ethoxymethyleneacrylonitrile by2,5-dimethoxy-α-ethoxymethylene-acetoacetanilide, a yellow pigment offormula ##SPC16##

is obtained which in varnishes and PVC has good fastness properties.

EXAMPLE 6

A solution of 35.6 parts of3-cyano-2,6-dihydroxy-5-formyl-4-methylpyridine in 145 parts of dimethylformamide is slowly added to a solution of 21.6 parts ofo-phenylenediamine in 140 parts of dimethyl formamide. The mixture issubsequently stirred at boiling temperature over the course of 3 hours,cooled and the precipitate is filtered off, washed with ethanol anddried at 80° in a vacuum. The resulting product of formual ##SPC17##

has a M.P. of 271°-274° with decomposition.

A solution of 11.7 parts of α-ethoxymethylene-acetoacetanilide in 40parts of dimethyl formamide is slowly added at 100° to a suspension of13.4 parts of the above compound in 95 parts of dimethyl formamide. Themixture is heated to 100°, stirred at this temperature over the courseof 30 minutes, and a solution of 12.5 parts of nickel acetatetetrahydrate in 115 parts of dimethyl formamide is slowly added. Thereaction mixture is stirred at 120° for 3 hours. After cooling, theprecipitate is filtered off, washed with ethanol and dried. The productis identical with the product of Example 4.

APPLICATION EXAMPLE

0.5 Parts of the pigment, obtained in accordance with Example 1, and 5parts of titanium dioxide pigment are added to a mixture consisting of

63 parts of a polyvinyl chloride emulsion,

32 parts of dioctyl phthalate,

3 parts of a commercial epoxy softener,

1.5 parts of a commercial stabilizer (barium-cadmium complex)

0.5 parts of a commercial chelator

and the whole is intimately mixed. The mixture is rolled at 160° for 8minutes in a roller mill with friction rollers (one roller rotates at 20r.p.m., the second at 25 r.p.m. ) to obtain a better distribution of thepigment. The mixture is subsequently extruded as a film of 0.3 mmthickness. The film is pigmented in a red shade. The dyeing has goodfastness to light and migration, and heat resistance.

In the following Table further pigments of formula Ia are indicatedwhich may be produced in analogy with the operating processes ofExamples 1 to 6. In all the Examples R₉ is hydrogen, except in Example50 where it is methyl.

                                      TABLE                                       __________________________________________________________________________    Exp.                                                                          No.                                                                              R.sub.10            R.sub.11     R.sub.12       Me.sub.1                                                                         Shade in                __________________________________________________________________________                                                          PVC                      7 --NHC.sub.6 H.sub.5                             Ni orange                   8 "                                "              "  "                        9                                  "              "  reddish yellow          10                     "            "              "  orange                  11 "                   "            --CH=CH--CH=CH--                                                                             "  reddish yellow          12 --NHC.sub.6 H.sub.5 "                           "  orange                  13 "                   "                           "  yellow                  14                     "            "              "  reddish yellow          15                                  --N*--N=C--    Ni yellow brown                                                ||                                                          C.sub.6 H.sub.5 CH.sub.3                  16 --NHC.sub.6 H.sub.5 "            "              "  "                       17 "                   "            --C= C--CO--NH*--                                                                            Cu "                                                           ||                                                          CH.sub.3 CN                               18 "                                "              Ni orange                  19 "                                "              "  "                       20 "                                "              "  reddish yellow          21 "                                "              "  orange                  22                                  "              "  yellow                  23                     "            "              "  reddish yellow          24                                  "              Ni "                       25                     "            "              "  "                       26                     "            "              "  "                       27                     "            "              "  "                       28                     "            "              "  "                       29                     "            "              "  "                       30                     "            "              "  "                       31 --CH.sub.3                       "              "  "                       32 --OCH.sub.3         "            "              "  "                       33 --OC.sub.2 H.sub.5  "            "              "  "                       34 --NH.sub.2          "            "              "  "                       35 --NHC.sub.6 H.sub.5              "              Ni "                       36                                  "              "  "                       37 --NHC.sub.6 H.sub.5                             "  orange                  38 "                                "              "  "                       39                                  "              "  red                     40                                  --C=C--CH=CH-- "  reddish yellow                                              |                                                                    OCH.sub.3                                 41                                  --C*H=CH--CH=CH--                                                                            "  "                                                           |                                                                    NO.sub.2                                  42                                  --C*=CH--C=CH--                                                                              "  "                                                           ||                                                          ClCl                                      43                                                 Ni "                       44                                                 "  "                       45                                                 "  "                       46 --NHCH.sub.3                     --C=CH--CH=CH--                                                                              "  "                                                           |                                                                    Cl                                        47 --NHC.sub.2 H.sub.5 "            --C=CH--CH=CH--                                                                              "  "                                                           |                                                                    Br                                        48                                  --C=C--CO--NH*--                                                                             "  "                                                           ||                                                          CH.sub.3 CN                               49                                  "              "  "                       50 --NHC.sub.6 H.sub.5              "              "  "                       __________________________________________________________________________

What is claimed is:
 1. A compound of formula I, ##SPC18##in which R₁ isalkyl, R₂ is alkylcarbonyl, alkoxycarbonyl or -CONR₆ R₇, R₃ is hydrogenor alkyl R₄ is an aromatic carbo- or heterocyclic bivalent radical boundthrough ortho or peri-positions R₅, together with the >C=C< group,signifies an aromatic carbo- or heterocyclic ring, R₆ is hydrogen oralkyl, R₇ is hydrogen, alkyl or a mono- or bi-nuclear aromatic carbo- orheterocyclic ring, and Me is a bivalent transition metal atom or zinc.2. A compound of claim 1, of formula Ia, ##SPC19##where R₉ is hydrogenor methyl, R₁₀ is C₁₋₂ alkyl, C₁₋₂ alkoxy or -NHR₁₃, R₁₁ is1,2-phenylene, unsubstituted or substituted as hereinafter set forth,1,2-, 2,3- or 1,8-naphthylene, 9,10-phenanthrylene, 5,6-acenaphthenyleneor a radical of formula (a), (b), (c), (d) or (e), ##SPC20## R₁₂signifies a radical of formula (f), (g), (h), (i) or (j), ##EQU6##wherein the asterisked atom is bound to the carbon adjacent the oxygenin formula Ia, radicals (f) and (g) being unsubstituted or substitutedas hereinafter set forth, R₁₃ signifies hydrogen, C₁₋₄ alkyl, naphthyl,benzimidazolonyl-5 or phenyl, or phenyl substituted by a total of up tothree substituents of which up to 3 are methyl, 2 are selected fromchlorine, bromine, nitro and C₁₋₂ alkoxy and up to 1 is selected fromC₁₋₂ alkylcarbonylamino, phenylcarbonylamino and phenylaminocarbonyl,which latter two radicals are unsubstituted or substituted ashereinafter set forth, R₁₄ is methyl or phenyl, R₁₅ is hydrogen, methylor phenyl, and Me₁ is nickel, copper, zinc or cobalt,any substitutedphenylene as R₁₁, any phenylcarbonylamino or phenylaminocarbonyl in R₁₃and any substituted radical (f) or (g) as R₁₂ being substituted by atotal of up to two substituents of which up to 2 are selected fromchlorine, bromine, methyl and C₁₋₂ alkoxy and up to 1 is selected fromcyano, hydroxy, nitro, C₁₋₂ alkoxycarbonyl, aminocarbonyl, C₁₋₂alkylaminocarbonyl, di-C₁₋₂ alkylaminocarbonyl, carboxyl, phenyl andphenoxy.
 3. A compound of claim 2, of formula Ib, ##SPC21##in which A ismethyl, C₁₋₂ alkoxy, --NH₂, C₁₋₂ alkylamino, benzimidazolonyl-5-amino orphenylamino, said phenylamino being unsubstituted or substituted by atotal of up to three substituents of which up to 3 are methyl, up to 2are selected from chlorine, bromine, nitro and C₁₋₂ alkoxy and up to 1is selected from C₁₋₂ alkylcarbonylamino, phenylcarbonylamino andphenylaminocarbonyl, the phenyls in said phenylcarbonylamino andphenylaminocarbonyl groups being unsubstituted or substituted by up totwo substituents selected from chlorine, bromine and C₁₋₂ alkoxy, Bsignifies unsubstituted 2,3-dihydroxyquinoxalinylene-6,7,benzidimazolonylene-5,6 or 1,2-phenylene, or 1,2-phenylene substitutedby a total of up to two substituents of which up to 2 are selected fromchlorine, bromine, methyl and C₁₋₂ alkoxy and up to 1 is selected fromcyano, hydroxy, nitro, C₁₋₂ alkoxycarbonyl, aminocarbonyl and carboxy, Dsignifies a radical (f), unsubstituted or substituted by up to twosubstituents of which up to 2 are selected from chlorine, bromine, andmethoxy and up to 1 is nitro; a radical (g'), ##SPC22##whereR₂₀ ishydrogen or carboxy, and R₂₁ is hydrogen, chlorine, bromine or nitro; aradical (i); in which R₁₄ is methyl; or a radical (j), in which R₁₄ ismethyl and R₁₅ is phenyl, and Me₂ is nickel or copper.
 4. A compound ofclaim 3, of formula Ic, ##SPC23##where A₁ is unsubstitutedbenzimidazolonyl-5-amino, unsubstituted phenylamino or phenylaminosubstituted by a total of up to three substituents of which up to 3 aremethyl, up to 2 are selected from chlorine, bromine, nitro, C₁₋₂ alkoxyand up to 1 is C₁₋₂ alkylcarbonylamino, phenylcarbonylamino andphenylaminocarbonyl, any phenyl moiety in said latter two radicals beingunsubstituted or substituted by up to two substituents selected fromchlorine, bromine and C₁₋₂ alkoxy, B₁ signifies unsubstitutedbenzimidazolonylene-5,6 or 1,2-phenylene, unsubstituted or mono bychlorine, bromine, methyl, methoxy and nitro, and D₁ is an unsubstitutedradical (f); a radical (g'), in which R₂₁ is hydrogen; a radical (h),where R₁₄ is methyl; or a radical (i).
 5. A compound of claim 4, offormula Id, ##SPC24##where A₂ is phenylamino, unsubstituted orsubstituted by one or two methoxy groups and/or by a chlorine or methyl,B₂ is unsubstituted benzimidazolonylene-5,6 or 1,2-phenylene,unsubstituted or mono-substituted by chlorine, methyl or methoxy, D₂ isa radical (g'), in which R₂₁ is hydrogen; a radical (h), in which R₁₄ ismethyl; or a radical (i), and
 6. A compound of claim 5, of formula##SPC25##
 7. A compound of claim 5, of formula ##SPC26##
 8. A compoundof claim 5, of formula ##SPC27##
 9. A compound of claim 5, of formula##SPC28##
 10. A compound of claim 5, of formula ##SPC29##
 11. A compoundof claim 5, of formula ##SPC30##
 12. A compound of claim 5, of formula##SPC31##
 13. A compound of claim 3, wherein A is phenylamino,unsubstituted or
 15. A compound of claim 3, wherein B is 1,2-phenylene,unsubstituted or
 16. A compound of claim 3, wherein B is unsubstituted22. A compound of claim 3, in which Me₂ is nickel.